The development of efficient and robust catalysts based on earth‐abundant and nontoxic materials is critical for the viability of the electrocatalytic conversion of CO2 into useful chemicals. Herein, we report a new class of electrocatalysts with incorporated mechanisms of their stabilization. A Cu electrode coated with a poly(4‐vinyl pyridine) film synthesizes formate at a faradaic efficiency of 40 % at an overpotential of −0.67 V, and its catalytic activity does not degrade after 30 h of operation. We attribute the outstanding catalytic properties of the new hybrid material to the formation of Cu–polymer complexes, as well as to new intrinsic mechanisms of the electrode stabilization offered by the N‐heteroaromatic polymer. This is the first report of CO2 electroreduction with copper–N‐heteroaromatic ligand complexes. More generally, our study offers a new simple strategy to design and prepare robust CO2 reduction electrocatalysts based on earth‐abundant metals.